Chemical compounds and process of treating textile materials therewith



United States Patent CHEMICAL COMPUUNDS AND PROCESS OF TREATING TEXTILEF/EATERIALS THERE- WITH Oscar P. Cohen, Newton, Mass, assignor toMonsanto Chemical Company, St. Louis, Mo., a corporation of Delaware NoDrawing. Application October 2, 1952, Serial No. 312,867

19 Claims. 01. 252-5375 The present invention relates to processes offinishing textile materials, particularly synthetic staple fibers oryarns, and it more particularly relates to processes of applying alubricant finish or a lubricant and anti-static finish to such textilematerials. The present invention also relates to novel chemicalcompounds which are especially suitable for use in the textile finishingprocesses of this invention.

It is one object of this invention to provide processes for treatingtextile materials, particularly synthetic staple fibers or yarns havinglow moisture pick up or adsorptivity to render them more amenable toprocessing operations such as spinning in the case of staple fibers, andweaving in the case of yarns or filaments.

It is a further object of this invention to provide textile materials,particularly synthetic staple fibers or yarns, having a low moisturepick up or adsorptivity, which have a lubricant finish or a lubricantand anti-static finish thereon.

It is a further object of this invention to provide novel textilefinishing compositions.

It is a further object of this invention to provide novel chemicalcompounds which are especially suitable for use in finishing textilematerials to provide such materials with a lubricant finish or alubricant and anti-static finish.

Still further objects and advantages of this invention will becomeapparent from the following description and the appended claims.

The present invention provides novel chemical compounds having thestructural formula:

where R is selected from hydrogen and methyl and ethyl radicals, R isselected from hydrogen and methyl, ethyl,

and

l I! C2114 \O C2H4/, O (L) R groups, R" is selected from saturated andunsaturated aliphatic hydrocarbon radicals consisting of carbon andhydrogen atoms and containing from 5 to 23 carbon atoms, x represents aninteger from 1 to 20, y represents an integer from 1 to 19 and x and ytaken together represent a whole number not exceeding 20. In general,compounds which are included in the scope of the above formula and whichcontain 9 and more oxyethylenc {OC2H4} units have relatively low meltingpoints and are normally liquids at room temperature. Moreover, suchcompounds are soluble or colloidally dispersible in water and thus maybe used in aqueous textile finishing compositions. On the other hand,compounds of the above formula which contain one but less than 9 oxy-2,727,004 Patented Dec. 13, 1955 where x is an integer of 1 to 20;compounds having the structural formula:

C2H4 0CiE[4},0 C n as where x and y are integers which taken togethertotal at least 2 but not more than 20; compounds having the structuralformula:

where x is an integer of l to 20; and the like.

The novel compounds of this invention may be prepared by firstcondensing 2 to 20 mols of ethylene 0xide with 1 mol of a sulfonamidehaving the structural formula:

R\ i) Ii 3 i where R and R have the same significance as in thestructural formula of the novel compounds of this invention,hereinbefore given, preferably in the presence of an alkaline condensingagent such as caustic soda, caustic potash or alkali metal alcoholatessuch as sodium ethylate. This reaction or condensation is preferablycarried out in a closed vessel at temperatures between about 70 and 200C., and at pressures ranging from atmospheric pressure to about 10atmospheres. The pressure decreases as the ethylene oxide enters intothe reaction. The above reaction or condensation provides compoundshaving the structural formula:

where R, R and x have the same significance as hereinbefore described.When R in the formula of the sulfonamide is hydrogen and at least 4 molsof ethylene oxide are employed, a mixture of a compound having thestructural formula described immediately above and a compound having thestructural formula:

where R, x and y have the same significance as hereinbefore given, isobtained. This mixture may be used in preparing the novel compounds ofthis invention.

As examples of sulfonamides which may be reacted or condensed withethylene oxide as described above may be mentioned benzene sulfonamidealso known as benzene sulfonic amide), toluene sulfonamide (also knownas toluene sulfonic amide), including the ortho and para isomers andmixtures thereof, dimethyl benzene sulfonamides, N-ethyl' toluenesulfonamjde and the like. Of these compounds, ortho or para toluenesulfonamide or mixtures thereof and N-ethyl toluene sulfonamide arepreferred as starting materials.

The; ethylene oxidersulfonamide condensation products hereinbeforedescribed, are reacted with aliphatic fatty'monocarboxylic acidscontainingv from 6 to 24 carhon: atoms and having the, structuralformula:

where R has the same significance as hereinbefore described to producethe novel compounds of this invention. About 1 mol of fatty acid isemployed for each hydroxyl group in the ethylene oxide-sulfonamidecondensation product, and depending on whether the monoor diester isdesired. This reaction is preferably carried out in the presence of aninert, water-soluble organic solvent as, for example, liquid aromatichydrocarbons such as benzene, toluene, xylene and the like, and; a smallamount of a strong acid esterification catalyst such as; a strongmineral acid as, for example, sulfuric or phosphoric acid or a strongorganicsulfonic acid such as toluene monosulfonic acid, naphthalenemonosulfonic acid or benzene monosulfonic acid or the like. Theesterification reaction is carried out at least at the boiling point ofwater with the removal of 1 mol of water per mol of fatty acid employed,and at atmospheric or subatniospheric pressure. The acid catalyst in thepr duct thus obtained is preferably neutralized with a base such assodium hydroxide, or, more preferably, with an organic base which issoluble in the organic solvent as, for example, morpholine, pyridine andquaternary ammonium hydroxides, toprovide a neutral product. Theorganic. solvent, if used, is then evaporated leaving the desiredproduct as the residue.

As examples of fatty acids which may be used in preparing the novel.esters of this invention maybe mentioned saturated fatty acids suchascaproic acid, capric acid, lauric acid, palmitic acid, stearic acid andthe like,

and unsaturated fatty acids such as oleic acid, linoleic acid, linolenicacid and the like.

Various changes may be made in the processes described above. Forexample, it is possible when the sulfonamide contains two reactivehydrogen atoms to replace one of such hydrogen atoms with one or moreoxyethylene -(-OCzH4-} groups and then esterify the resultingmono-alcohol compound with 1 mol, of the fatty acid. This compound maybe used as such or it may be further condensed through the remainingactive hydrogen with ethylene oxide tointroduce one or more oxyethylenegroups. The resulting compound may be used as such or it may be, furtheresterified with 1 mol of one of the fat y acids. to produce a diester.Other modifications of the processes described above will be apparent tothose skilled in the art.

The textile finishing process of this invention comprises applying to atextile material a textile, finishing composition comprising a compoundhaving the following structural formula:

(Hi-R" where R is selected from hydrogen and methyl and ethyl groups, Ris selected from hydrogen and methyl, ethyl and groups, R" is selectedfrom saturated and unsaturated aliphatic hydrocarbon radicals consistingof carbon and hydrogen atoms and containing from 5 to 23 carbon atoms,11 represents 0 and integers from 1 to 20, m represents 0 and integersfrom 1 to 20, and n and m taken together represent 0 and integers, thetotal of which does not exceed 20. The compounds represented by theabove structural formula include the novel compounds of this invention,and they also. include known chemical compounds such as N, N-di-betahydroxyethyl benzene sulfonamide distearate and N-beta-hydroxyethylbenzene sulfonamide stearate which have not been suggested heretofore.for use in the finishing of textile materials.

The compounds, defined inthe. preceding paragraph are. preferablyapplied to, textile materials in an amount sufiicient to lubricate suchmaterials or to lubricate and inhibit the formation of charges of staticelectricity on such materials. Satisfactory results, for these purposes,are obtained, in general, by applying: about 0.1 to 5% by weight andpreferably about 0.2 to 3.5% by weight of these compounds based on theweight of the. textile materials. These compounds per se may be applieddirectly to the textile, material in the liquid state, using hea t,. ifnecessary, to melt them prior tov application. However, it is preferredto incorporate these compounds in, a textile finishing composition whichcontains water, mineral oil or an emulsion of mineral oil and water asthe sole or primary liquid other than the compounds per se. When aqueoustextile finishing compositions or emulsions of waterand mineral oil areemployed it is preferli d' to use those ester compounds which are sol- U21? OI colloidally dispersible in water, particularly those, estercompounds, as hereinbefore defined, which contain 9 or more oxyethylene+O?C2H4 groups in the, molecule. Compounds which contain less than 9oxyethylene groups are more soluble in mineral or hydrocarbon oils andare'not generally soluble or colloidally dispersible in water per se.Therefore, these com.- pounds are preferably applied to textile frommineral oil compositions or emulsion of mineral oil and water. However,they may be dispersed in aqueous compositions with the aid ofemulsifying agents if necessary, and may thus be applied to textilematerials from such compositions.

The textile finishing compositions described above preferably containfrom about 0.1 to 10% by weight of the ester compounds hereinbeforedefined, and the remainder preferably consists of water, a water-mineraloil emulsion or a mineral oil. However, such compositions may alsocontain the usual amounts of conventional textile treating agents suchas colloidal silica, thermosetting resins, thermoplastic resins, wettingor emulsifying agents or the like.

These textile finishing compositions may be applied to the textilematerials in various ways. Thus they may be applied by dipping orimmersing the textile materials therein followed, if desired, bysqueezing between rolls, centrifuging or the like, or they may beapplied to textile materials by spraying or dripping the compositions onthe materials. Such compositions may also be applied to textilematerials by passing the materials over one or more wicks or rolls whichare covered with a film of the composition. Various other procedures tqrapplying such compositions to textiles will be apparent to those skilledin the art.

The ester compounds, hereinbefore defined, may be incorporated directlyinto synthetic textile staple fibers or yarns and filaments during themanufacture of such textiles. For example, in those instances where thesynthetic textile staple fiber or yarn or filament is prepared from aspinning dope such as a solution of cellulose acetate in acetone, theester compound may be incorporated in the spinning dope or solutionwhich is then extruded to form the textile staple fibers or filaments.

The novel compounds or textile finishing compositions of this inventionmay be applied to a large variety of textile materials, particularlythose materials which require a lubricant or which normally acquirestatic electric charges due to the friction developed during theirprocessing. For example, such compounds or compositions may be applied,prior to spinning, to natural fibers of vegetable origin such as cotton,linen, rann'e or the like or to nautral fibers of animal origin such aswool, alpaca, camels hair or the like, or they may be applied to yarnsor-fabrics composed wholly or partly of such natural fibers. Thecompounds or compositions of this invention may also be applied toregenerated cellulose staple fibers, yarns or fabrics. In suchapplications the ester compounds serve, primarily, the function oflubricating the fibers, yarns or fabrics, although they also inhibit theformation of static electricity on such textile materials. However, thelatter phenomenon is not too marked since the natural fibers pick up andretain moisture quite readily and hence do not accumulate staticelectricity charges to a marked extent and do not, as a general rule,require the application of compounds having anti-static properties.

The textile finishing compositions or compounds are particularlyeffective as lubricants and anti-static agents on synthetic staplefibers and yarns or filaments which have low moisture pick up oradsorptivity. The term synthetic textile materials as used herein and inthe appended claims is intended to include staple fibers and yarnsprepared from fiber-forming synthetic polymers prepared by polymerizinga suitable vinyl or vinylidine monomer per se or a suitable vinyl orvinylidine monomer and an unsaturated organic compound copolymerizabletherewith and having at least one -C=C- group in the molecule, forexample, polymers such as polyacrylonitrile, copolymers of acrylonitrileand vinyl chloride, copolymers of acrylonitrile and vinyl pyridine,polyvinylidine chloride, copolymers of vinylidine chloride and vinylchloride and the like, and is also intended to include fiber-formingpolymers prepared by condensing an alkylene diamine and an aliphaticdibasic acid, for example, polymers such as polyhexamethyleneadipamide,polyhexamethylene-sebacamide and the like; and is also intended toinclude fiber-forming polymers prepared by condensing terephthalic acidwith polyhydric alcohols such as ethylene glycol, diethylene glycol andthe like; and is also intended to include water-insoluble fiber-formingcellulose esters such as cellulose acetate, cellulose propionate,cellulose butyrate and the like. The term synthetic textile materialsdoes not, however, include hydrophilic staple fibers or yarns ofregenerated cellulose prepared by regenerating cellulose xanthate orcuprammonium solutions or dopes.

Since the compounds or compositions of this invention exhibitanti-static properties they are particularly effective in this respectwhen they are applied to staple fibers or unspun fibers prior toprocessing such fibers into Webs, slivers, yarns or the like, and theyare also particularly effective when applied to yarns or filamentsimmediately after the formation of such yarns or filaments and prior tofurther processing thereof such as twisting, coning, weaving or thelike. The compounds or compositions of this invention are most etfectiveas lubricants and anti-static agents when they are applied to staplefibers or yarn containing from about to 100% by weight of the syntheticfiber-forming materials, which term includes the cellulose esters butex- G cludes regenerated cellulose, defined in the preceding paragraph,and the treatment of such textile materials is preferred.

The particular composition used will depend on the particular textilematerial which is to be treated and the form of the textile material,that is, whether it is in the form of fibers, yarns or fabrics. Forexample, in treating cellulose acetate fibers and blends of celluloseacetate fibers and other synthetic staple fibers, as hereinbeforedefined, it is customary in most cases to use mineral oil or hydrocarbonoil compositions, and hence such compositions containing the estercompounds are preferably employed on such fibers. On the other hand, intreating animal fibers, vegetable fibers, regenerated cellulose staplefibers and polyhexamethylene-adipamide staple fibers or blends thereof,it is desirable to use aqueous compositions or emulsions of water andmineral oil or vegetable oil. Similar compositions are used in treatingyarns or fabrics of these textile materials.

The preferred ester compounds for use in aqueous compositions oremulsion of water and mineral oil are those having the followingstructural formula:

groups, R is the hydrocarbon chain of oleic acid, x represents aninteger from 9 to 20 and x and y taken together represent integerstotalling at least 9 but not exceeding 20.

The preferred ester compounds for use in mineral oil compositions arethose having the following structural formula:

i l r EXAMPLE I (a) Preparation of ester compound One mol of a mixtureof o-toluene sulfonamide and p-toluene sulfonamide was condensed with 4mols of ethylene oxide at atmospheric pressure and at a temperature of70 C. The temperature of the reaction mass soon rose to C. due to theheat of reaction and the reaction mass was maintained at thistemperature until substantially all of the ethylene oxide had reacted.The resulting product was dispersed in xylene. One mol of lauric acidwas then added to the resulting dispersion along with 0.02 mol ofp-toluene sulfonic acid which was employed as an esterificationcatalyst. The resulting mixture was heated to C., and the Water formedduring the reaction was removed by distillation at atmospheric pressureinto a water trap until no more water was evolved. The resulting productin the solutioncon- 7 'pi'hnsnly of a mixture of a compound having Thesecompounds, after evaporation of the Xylene, are recovered a wax-likematerials at room temperature (about 70 F.) and-they are ins luble inwater, but soluin mineral or hydrocarbon oils;

(b) Treatment-f textile material Five parts of the mixture "of compoundsprepared as described above were dissolved in I00 parts of low'viscosity mineral; oil. Wicks were dipped into the resulting solutionand filaments of cellulose acetate, as obtained directly by dry spinninga cellulose acetate-acetone dope, were passed over these wicks and incontact therewith. The amount of ester compounds depositedon thefilament was about 1% based on the dry filament weight. The resultingyarn was well lubricated and did not accumulate static electricalcharges during subsequent processing operations such as coming orWeaving.

EXAMPLE II (a) Preparation of ester compound One mol of 'p toliren'e"sulfonaniide was condensed with two mols of ethylene oxide atatmospheric pressure and i at a temperature of 70 C. The temperature ofthe reaction mass soon rose to 130. Qt due to heat of reaction andthereaction mass was maintained atthis temperature until substantially allof the ethylene oxide had reacted. The resultingproduct consistsprimarily of a compound "having the formula:

This compound, which has a melting point of 72 C., was separated fromother compounds in the product by fractional distillation and was thenesterified with 1 mol of acid using 0;02 mol of p-toluene 'sulfonic acidas the esterification catalyst. The esterificatio'n was carried out inxylene at a temperature of 140 C., and the water formed during the'esterification was removed by distillation into a water trap until nomore water was evolved. The resulting product in the solution consistedprimarily of a compound having the formula:

this compound, which was a liquid at room temperature,

oils;

(b) Treatment of textile materials;

One part of the compound describedimmediately above was dissolved inparts of water and the resulting solution was placed in a container inwhich a partially submerged roller was slowly and continuously rotating;The surface of the roller was thus provided with a continuous film ofthe solution. Filaments of viscose (regenerated cellulose) rayon werecoustant;ly brought into contact with the top surface of the roller.About of the compound, based on the dry filament weight, was :depositedon the filaments in this manner. The compound was an e'fiectivelubricant for the filaments.

Polyhexamethylene-adipamide filaments were treatedin the same manner asthe viscose rayon filaments in preceding paragraph. The treatedfilamentswerenot only lubricated, but also did not accumulate static electricalcharges during subsequent processing of the filaments. I

(a) Preparation of ester compound One mol of p-toluene sulfon'amide wascondensed four mols of the ethylene oxide using the procedure scribed inthe first paragraph of Example I. Thematiing product was then esterifiedwith 1- mail o'f olei'c acid using the procedure set forth in thefirstaragraph of Example I. Xylene was evaporated from thfresultiflgsolution and the product thus obtained was the'ii densed with 5 mols ofethylene oxide at atmospheric.

pressure in the presence of 1%- of sodium ethylafe and at a temperatureof 70 C. The temperature soon rose to C. and "the reaction mass wasmaintained at this temperature ninil substantially all of ethylene oxidehad reacted. This product was then esterifie'uwith '1 mol of oleic acidin the presence of 0.0211161 'of-p toluene sulfonic acid as anesterific'ation catalyst. The s'terifi'ation was carried out in xyleneat atmospheric pressure and at a temperature of Q,- and the water tonnesduring the reaction was removed by distillation into a water trap untilsubstantially no more water was evorvea. The product consisted primarilyof a having the formula:

This compound is water-dispersible.

When the compound is dispersed in an aqueous tion containing about 8% byweight of a water-soluble melamine formaldehyde orurea-formaldehydepl'ecolr densate in an 'amount of about 10 to 20%onjthe of the precondensate, the resulting dispersion is-e spec ia1lysuitable for use in preparing glazed textile fabrics the compoundprovides good lubrication during the 51:2- ing operation.

This compound when dispersed in a 15% siliea-aquasol in amounts of 0.5to 3% by weight and then applied to cotton fibers prior to spinning,imparts some-lubricating and anti-static effects to the fibers and alsoreduces tendency of the silica to dust from the fibers dry weight of thefilament, thus depositingabout 033915 of the compound onthe'filament'weight. ThgTCSl-lhifi soluble in water and onl slightlysoluble in 1% filaments were not only lubricated, but also did notaccumulate static charges during subsequent processing.

EXAMPLE V The palmitate ester of N-hydroxyethyl toluene sulfonamide wasdissolved in a spinning solution of cellulose acetate in acetone in anamount of 2% based on the weight of cellulose acetate. The spinningsolution was then extruded through a spinneret into warm dry air. Afterall of the acetone had evaporated from the resulting filaments, thefilaments were free of static electrical charges during subsequentprocessing of the filaments.

Various changes may be made in the compositions and processes describedherein as will be apparent to those skilled in the art to which thisinvention appertains without departing from the spirit and intent ofthis invention. Accordingly, it is intended that this invention is notto be restricted except by the scope of the appended claims' What isclaimed is:

l. A chemical compound having the structural formula:

where R is selected from the group consisting of hydrogen and methyl andethyl radicals, R is selected from the group consisting of hydrogen andmethyl, ethyl,

and

where x is an integer of l to 7.

3. A chemical compound having the structural formula:

where x and y represent integers of at least 1 and which when takentogether represent a whole number not exceeding 20.

4. A chemical compound having the structural formula:

where x and y represent integers of at least 1 and which when takentogether represent a whole number not exceeding 20.

1o 5. A chemical compound having the structural formula:

o o olmoogn, O iL-GUHa where x and y represent integers of at least 1and which when taken together represent a whole number not exceeding 20.

6. A chemical compound having the structural formula:

where R is selected from the group consisting of hydrogen and methyl andethyl radicals, R is selected from the group consisting of hydrogen andmethyl, ethyl,

and

radicals, R is selected from the group consisting of saturatedand'unsaturated aliphatic hydrocarbon radicals con sisting of carbon andhydrogen atoms and containing from 5 to 23 carbon atoms, x represents aninteger from 1 to 7, 3' represents an integer of at least 1 and x and ytaken together represent integers totalling from 2 to 8, said compoundbeing soluble in said mineral oil,,but being insoluble andnon-dispersible in water.

8. A process of finishing textile materials which comprises applying tosaid textile materials a compound having the structural formula:

where R is selected from the group consisting of hydrogen and methyl andethyl radicals, R is selected from the class consisting of hydrogen andmethyl, ethyl,

and

groups, R" is selected from the group consisting of saturated andunsaturated aliphatic hydrocarbon radicals consisting of carbon andhydrogen atoms and containing from 5 to 23 carbon atoms, n represents 0and integers from 1 to 7, m represents 0 and an integer of at least 1and n and m taken together represent 0 and integers the total of whichdoes not exceed 8, said compound being soluble in mineral oil, but beinginsoluble and non-dispersible in water.

9. A process as in claim 8, but further characterized in that saidcompound is applied from a textile finishing composition comprising saidcompound and mineral oil.

t- A prewa as in claim: 8. but further. char c riz in that the textilematerials are composed of from about 20 to 100% by weight of synthetictextile materials.

11. A process as in claim 8, but further characterized in thatthetextile materialsarecomposed of. from about 20 to 100% by weight ofcelluloseacetate textile materials.

12. A process as inclaim 8, but further characterized in that thetextile materials are composed of from about 2.0. to 100% by weight ofpolyhexamethylene-adipamide textile materials;

13. A process as" in claim- 8', but further characterized in that thetextile materials are composed of from about 20' to 100% by weightof'polyacrylonitrile;

14. A process of lubricating textile materials which comprises applyingto said textile materials.v an aqueous composition comprising from about0.1 to 10% by weight of a water-soluble: to colloi'dally dispersedcompound having the structural' formulaz 'where Z is. selected from thegroup consisting of hydrogen and methyl, ethyi,

and

O walw-mmLoJLnv groups, R" is selected from the group consisting of.satw rated and unsaturated aliphatic hydrocarbon radicals consisting ofcarbon and hydrogen atoms and containing from to 23 carbon atoms, x isan integer from 9 to 20 and x and y taken together are integerstotallingat least 9 but notexceeding 20, said composition. beingsupplied in an amount sutficient to: deposit from about 0.1 to, 5% ofsaid compound based on the-dry textile materials.

15. A. processas in. claim. 14,. but. further characterized in that R inthe formula; of said compound is the hydrocarbonchain of oleieacid.

16. A.- process-of: lubricating textile materials which comprisesapplying to' said textile materials-a mineral. oil solution of fromabout 0:1 to; 10% by weight of a compound: havingthe; formula:

where Z is selected from the group consisting of hydrogen methyl; ethyl,

and

l C2H -O.C -@O-- -R 4 r34! 7 I groups, R is selected from the. groupconsisting of saturated and unsaturated aliphatic hydrocarbon radicalsconsisting of carbon and hydrogen atoms and coutainingfrom 5 to 23,carbon atoms, x is an integer from 1; to 7 and: and8 y taken togetherrepresent integers totalling from 2 to 17. A process, according to claim16, but filrther characterized in that the R" in the formula of saidcompound is' the hydrocarbon chain of oleic acid,

18. An article of manufacture comprising a-textile ma terial havingthereon a compound having the structural formula:

where R is selected from the group consisting of hydrogen and methyl andethyl groups, R" is selected from the group consisting of hydrogen,methyl, ethyl,

and

R" is selected from the group consisting of saturated and unsaturatedaliphatic hydrocarbon radicals consisting of hydrogen and carbon atomsand containing from 5 to 23 References Cited in the file of this patentUNITED STATES PATENTS 1,970,578 Schoelleret a1 Aug. 21, 1934 2,002,613Orthner et al May 23, 1935 2,353,694 De Groote et a1 July 18, 19442,496,650 Aelony Feb. 7,1950

2,496,651 Aelony ...Feb. I, 1250- FOREIGN PATENTS 380,851 Great BritainSept. 12, 1932

7. A TEXTILE FINISHING COMPOSITION COMPRISING A MINERAL OIL AND ACOMPOUND HAVING THE STRUCTURAL FORMULA: